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Monomer reactivities in anionic copolymerization are the opposite of those in cationic copolymerization. Reactivity is enhanced by electron-withdrawing substituents that decrease the electron density on the double bond and resonance stabilize the carbanion formed. Although the available data are rather limited [Bywater, 1976; Morton, 1983; Szwarc, 1968], reactivity is generally increased by substituents in the order



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The reactivity of monomers with electron-releasing substituents in anionic copolymerization is nil. Correlation of reactivity in copolymerization with structure has been achieved in some studies [Favier et al., 1977; Shima et al., 1962]. The reactivities of various substituted styrenes and methacrylates in anionic polymerization, as well as the reactivities of various vinyl

+ [ac(k) , a~(k')].





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ethers in cationic polymerization, have been correlated with the 1H and 13C chemical shifts of monomer [Hatada et al., 2002]. The general characteristics of anionic copolymerization are very similar to those of cationic copolymerization. There is a tendency toward ideal behavior in most anionic copolymerizations. Steric effects give rise to an alternating tendency for certain comonomer pairs. Thus the styrene p-methylstyrene pair shows ideal behavior with r1 5:3, r2 0:18, r1 r2 0:95, while the styrene a-methylstyrene pair shows a tendency toward alternation with r1 35, r2 0:003, r1 r2 0:11 [Bhattacharyya et al., 1963; Shima et al., 1962]. The steric effect of the additional substituent in the a-position hinders the addition of a-methylstyrene to a-methylstyrene anion. The tendency toward alternation is essentially complete in the copolymerizations of the sterically hindered monomers 1,1-diphenylethylene and trans-1,2-diphenylethylene with 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene [Yuki et al., 1964]. 6-4b-2 Effects of Solvent and Counterion

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Nov 8, 2012 · PDF Focus.Net - How to convert PDF to Word using C#. SautinSoft.Duration: 4:17 Posted: Nov 8, 2012

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Monomer reactivity ratios and copolymer compositions in many anionic copolymerizations are altered by changes in the solvent or counterion. Table 6 12 shows data for styrene isoprene copolymerization at 25 C by n-butyl lithium [Kelley and Tobolsky, 1959]. As in the case of cationic copolymerization, the effects of solvent and counterion cannot be considered independently of each other. For the tightly bound lithium counterion, there are large effects due to the solvent. In poor solvents the copolymer is rich in the less reactive (based on relative rates of homopolymerization) isoprene because isoprene is preferentially complexed by lithium ion. (The complexing of 1,3-dienes with lithium ion is discussed further in Sec. 8-6b). In good solvents preferential solvation by monomer is much less important and the inherent greater reactivity of styrene exerts itself. The quantitative effect of solvent on copolymer composition is less for the more loosely bound sodium counterion. Copolymerizations of nonpolar monomers with polar monomers such as methyl methacrylate and acrylonitrile are especially complicated. The effects of solvent and counterion may be unimportant compared to the side reactions characteristic of anionic polymerization of polar monomers (Sec. 5-3b-4). In addition, copolymerization is often hindered by the very low tendency of one of the cross-propagation reactions. For example, polystyryl anions easily add methyl methacrylate but there is little tendency for poly(methyl methacrylate) anions to add styrene. Many reports of styrene methyl methacrylate (and similar comonomer pairs) copolymerizations are not copolymerizations in the sense discussed in this chapter.

[ac(k), a~(k')] = 8(k - k')

TABLE 6-12 Effect of Solvent and Counterion on Copolymer Composition in Styrene Isoprene Anionic Copolymerizationa,b % Styrene in Copolymer for Counterion Li Na 66 66 77 75 80 15 15 59 68 80

1 -t -k . 1 + - \1 + r \ ' e-''kL .c*(k) coskL 0-+0+ k' - k + t'8 hm 7r 1 -t1 + - 11 + r I -k e ik'L , (k') cos k, . k - k' - t.8 L 0-+0+ hm 7r

Fig. 2-2 Polyesteri cation of adipic acid with diethylene glycol at 109 C catalyzed by 0.4 mol% p-toluenesulfonic acid. After Solomon [1967] (by permission of Marcel Dekker, New York) from the data of Flory [1939] (by permission of American Chemical Society, Washington, DC).

In addition to changing the text s font and size, you can change its colour. You might do so to make the text better stand out against the background or to coordinate with colours used in other slide elements such as photographs. You can change the text colour using a number of methods. One is to select a colour from the Font Color button on the Home tab; another is to launch the Colors dialog box and select a colour from the palette that appears. In addition, you can apply your own custom colour to text.

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To put it simply, no. There is no way to convert it to a DOC file using iTextSharp . It only supports the reading and generating of PDF files.

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